EP2876439A1 - Phase stationnaire - Google Patents
Phase stationnaire Download PDFInfo
- Publication number
- EP2876439A1 EP2876439A1 EP13822750.9A EP13822750A EP2876439A1 EP 2876439 A1 EP2876439 A1 EP 2876439A1 EP 13822750 A EP13822750 A EP 13822750A EP 2876439 A1 EP2876439 A1 EP 2876439A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- stationary phase
- silica gel
- surface area
- specific surface
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000005526 G1 to G0 transition Effects 0.000 title claims abstract description 97
- 229920000642 polymer Polymers 0.000 claims abstract description 122
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims description 50
- 238000004808 supercritical fluid chromatography Methods 0.000 claims description 25
- -1 polyethylene terephthalate Polymers 0.000 claims description 24
- 229920000728 polyester Polymers 0.000 claims description 20
- 239000004695 Polyether sulfone Substances 0.000 claims description 13
- 229920006393 polyether sulfone Polymers 0.000 claims description 13
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 12
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 12
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 11
- 229920002492 poly(sulfone) Polymers 0.000 claims description 7
- 229920000515 polycarbonate Polymers 0.000 claims description 6
- 239000004417 polycarbonate Substances 0.000 claims description 6
- 230000001965 increasing effect Effects 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 85
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 69
- 239000000741 silica gel Substances 0.000 description 67
- 229910002027 silica gel Inorganic materials 0.000 description 67
- 238000000926 separation method Methods 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 238000000034 method Methods 0.000 description 30
- 239000002904 solvent Substances 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 239000011148 porous material Substances 0.000 description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 21
- 239000000126 substance Substances 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 17
- 239000012071 phase Substances 0.000 description 15
- ZPZDIFSPRVHGIF-UHFFFAOYSA-N 3-aminopropylsilicon Chemical compound NCCC[Si] ZPZDIFSPRVHGIF-UHFFFAOYSA-N 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000004128 high performance liquid chromatography Methods 0.000 description 12
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 125000001424 substituent group Chemical group 0.000 description 11
- 125000005580 triphenylene group Chemical group 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 238000004587 chromatography analysis Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000000499 gel Substances 0.000 description 8
- 238000004811 liquid chromatography Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- OIAQMFOKAXHPNH-UHFFFAOYSA-N 1,2-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 OIAQMFOKAXHPNH-UHFFFAOYSA-N 0.000 description 7
- 238000007792 addition Methods 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000000969 carrier Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229930184652 p-Terphenyl Natural products 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000012856 packing Methods 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- ONDSBJMLAHVLMI-UHFFFAOYSA-N trimethylsilyldiazomethane Chemical compound C[Si](C)(C)[CH-][N+]#N ONDSBJMLAHVLMI-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- RWQUWTMOHXGTNN-UHFFFAOYSA-N 9-n,10-n-bis(4-butylphenyl)-9-n,10-n-bis(4-methylphenyl)phenanthrene-9,10-diamine Chemical compound C1=CC(CCCC)=CC=C1N(C=1C2=CC=CC=C2C2=CC=CC=C2C=1N(C=1C=CC(C)=CC=1)C=1C=CC(CCCC)=CC=1)C1=CC=C(C)C=C1 RWQUWTMOHXGTNN-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- 150000003462 sulfoxides Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CWILMKDSVMROHT-UHFFFAOYSA-N 1-(2-phenanthrenyl)ethanone Chemical compound C1=CC=C2C3=CC=C(C(=O)C)C=C3C=CC2=C1 CWILMKDSVMROHT-UHFFFAOYSA-N 0.000 description 2
- DQFWGPPCMONVDS-UHFFFAOYSA-N 1-anthracen-2-ylethanone Chemical compound C1=CC=CC2=CC3=CC(C(=O)C)=CC=C3C=C21 DQFWGPPCMONVDS-UHFFFAOYSA-N 0.000 description 2
- NXXNVJDXUHMAHU-UHFFFAOYSA-N 1-anthracen-9-ylethanone Chemical compound C1=CC=C2C(C(=O)C)=C(C=CC=C3)C3=CC2=C1 NXXNVJDXUHMAHU-UHFFFAOYSA-N 0.000 description 2
- JKVNPRNAHRHQDD-UHFFFAOYSA-N 1-phenanthren-3-ylethanone Chemical compound C1=CC=C2C3=CC(C(=O)C)=CC=C3C=CC2=C1 JKVNPRNAHRHQDD-UHFFFAOYSA-N 0.000 description 2
- UIFAWZBYTTXSOG-UHFFFAOYSA-N 1-phenanthren-9-ylethanone Chemical compound C1=CC=C2C(C(=O)C)=CC3=CC=CC=C3C2=C1 UIFAWZBYTTXSOG-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VBWFYEFYHJRJER-UHFFFAOYSA-N methyl 4-(hydroxymethyl)benzoate Chemical compound COC(=O)C1=CC=C(CO)C=C1 VBWFYEFYHJRJER-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002987 phenanthrenes Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 102000040430 polynucleotide Human genes 0.000 description 2
- 108091033319 polynucleotide Proteins 0.000 description 2
- 239000002157 polynucleotide Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 1
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- CJKOPYCBHDMAFY-UHFFFAOYSA-N 2-chloroethoxy-dimethoxy-(2-phenylethyl)silane Chemical compound ClCCO[Si](OC)(OC)CCC1=CC=CC=C1 CJKOPYCBHDMAFY-UHFFFAOYSA-N 0.000 description 1
- VNJOEUSYAMPBAK-UHFFFAOYSA-N 2-methylbenzenesulfonic acid;hydrate Chemical compound O.CC1=CC=CC=C1S(O)(=O)=O VNJOEUSYAMPBAK-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- LFASIQLVFCSCCU-UHFFFAOYSA-N 4-(4-chlorophenyl)sulfonylphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 LFASIQLVFCSCCU-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- BHWMWBACMSEDTE-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)cyclododecyl]phenol Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCCCCCCCC1 BHWMWBACMSEDTE-UHFFFAOYSA-N 0.000 description 1
- ICYDRUIZSPKQOH-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)decyl]phenol Chemical compound C=1C=C(O)C=CC=1C(CCCCCCCCC)C1=CC=C(O)C=C1 ICYDRUIZSPKQOH-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- RJWBTWIBUIGANW-UHFFFAOYSA-N 4-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C=C1 RJWBTWIBUIGANW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
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- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
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- GLBQVJGBPFPMMV-UHFFFAOYSA-N sulfilimine Chemical compound S=N GLBQVJGBPFPMMV-UHFFFAOYSA-N 0.000 description 1
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- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
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- 238000013519 translation Methods 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
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Images
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
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- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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Definitions
- the present invention relates to chromatographic technology.
- the present invention more particularly relates to a stationary phase for use in chromatography.
- Chromatography is the most effective means among methods for the analysis of the components of a mixture and their contents and for their separation and purification. Chromatography performs the separation of different substances by utilizing the substance-specific distribution ratio (also understood as the adsorption equilibrium) between a porous solid (the stationary phase) that is spatially immobilized in a column or a tube known as a capillary, and a fluid (the moving phase) that moves in the spaces in the porous solid.
- substance-specific distribution ratio also understood as the adsorption equilibrium
- a porous solid the stationary phase
- a fluid the moving phase
- Gas chromatography and liquid chromatography are typical here. A gas is used as the moving phase in the former.
- Liquid chromatography uses a liquid as the moving phase and can be applied to most substances assuming the selection of a suitable moving phase. Still, since liquids generally have high viscosities, limits are imposed by the increase in the viscous resistance when the generation of excellent separation is sought using a long column or capillary.
- Supercritical fluid chromatography was invented as a technology that can overcome the shortcomings of both gas chromatography and liquid chromatography.
- Supercritical fluid chromatography utilizes the characteristics of a supercritical or subcritical fluid, i.e., it dissolves other compounds much better than a gas and has a lower viscosity and a higher diffusion rate than a liquid.
- SFC using carbon dioxide as the supercritical fluid is generally employed based on safety and device considerations, and its use is gradually becoming more widespread.
- chromatography that uses electrical attraction and so-called thin-layer chromatography (a variant of liquid chromatography), in which paper or particles are consolidated in a thin layer, are available, but their range of application is not very broad.
- the typical modes for liquid chromatography are normal-phase chromatography, which uses the combination of a high-polarity stationary phase and a low-polarity stationary phase, and reversed-phase chromatography, in which these polarities are reversed.
- HILIC in which both phases are polar, has also been receiving attention quite recently.
- chromatographies based on specific interactions are also known, such as ligand-exchange chromatography, which utilizes metal ion/ligand interactions, and affinity chromatography, which utilizes biochemical interactions. Their characteristics and separation mechanisms are generally understood, and their technical advances mainly concern improvements in particle shape in order to improve the separation efficiency.
- the stationary phases used in conventional liquid chromatography have generally been also utilized as the stationary phase (also referred to as the column packing) in SFC.
- these are silica gels or silica gels that have undergone surface modification with various atomic groups.
- the modifying group may contain a saturated alkyl chain in various chain lengths; or may be a modifying group in which a condensed polycyclic aromatic hydrocarbon group or one or two benzene rings are bonded via an alkyl chain or an alkyl chain that includes the amide bond or ether linkage; or a modifying group in which the characteristic feature is a halogen-substituted benzene ring; or a modifying group in which a halogenated alkyl group is bonded; or a modifying group in which a polar group, e.g., the 2,3-dihydroxypropyl group, CN group, or NH 2 group is bonded; or may be a high molecular weight modifying group in the form of crosslinked polystyrene, polyvinyl alcohol, or polyethylene glycol.
- a polar group e.g., the 2,3-dihydroxypropyl group, CN group, or NH 2 group
- carbon having a graphite structure is also a special stationary phase.
- (2-pyridyl)ethyl group-bonded stationary phases referred to as 2-ethylpyridine
- 2-ethylpyridine are frequently used in SFC; their use is preferred because they provide sharp peak elution even for basic compounds, which undergo tailing and give broad peaks with ordinary stationary phases.
- Nonpatent Document 2 the retention trends for various compounds are similar and not a few stationary phases also exhibit no difference in characteristics. It is within this context that the present inventors, recognizing that the ability to discriminate among molecules having similar structures is a necessary condition, have diligently pursued the development of SFC stationary phases.
- polysaccharide-type stationary phases for chiral separation are also used in SFC and are utilized in chiral separations in practice (for example, Nonpatent Document 3).
- Polysaccharide derivatives are also provided with an excellent capacity to distinguish molecular structures outside of chiral separations, but can be difficult to use, because their selectivity range is too large and the separation of optical isomers becomes entangled.
- Nonpatent Document 4 a so-called vinyl polymer, e.g., a divinylbenzene/styrene copolymer and so forth, as packing is disclosed in Patent Document 1.
- Patent Document 2 discloses polystyrene beads for polynucleotide separation by liquid chromatography and also provides polyesters as an example thereof.
- a nonporous spherical body such as that disclosed in Patent Document 2
- retention may occur with relatively strongly polar polymers, such as the polynucleotides that are the separation target in the cited invention, while ordinary low molecular weight compounds cannot be retained - or strong tailing is produced even when retention does occur - and a practical analytical method is thus not obtained.
- Patent Document 1 Japanese Patent No. 3,858,509
- Patent Document 2 Japanese Translation of PCT Application No. 2002-506426
- Non-patent Document 1 C. West et al., J. Chromatogr. A, 1203(2008) 105
- the present invention solves the problems identified above and has as an object the introduction of a stationary phase that increases the number of column stages and that exhibits an excellent molecular discrimination ability.
- the present inventors discovered that the number of column stages can be increased and an excellent molecular discrimination ability can be realized by a stationary phase that contains a polymer having in the main chain repeat units an aromatic ring that forms a portion of the main chain and a bipolar atomic group that forms a portion of the main chain, wherein the stationary phase has a specific surface area of 5 to 1000 m 2 /g.
- the present invention was achieved based on this discovery.
- the present invention is as follows.
- the present invention can provide a stationary phase that increases the number of column stages and that has an excellent molecular discrimination ability.
- the present invention is a stationary phase that contains a polymer that has in the main chain repeat units an aromatic ring that forms a portion of the main chain and a bipolar atomic group that forms a portion of the main chain, wherein its specific surface area is 5 to 1000 m 2 /g.
- the stationary phase denotes a material in a chromatographic method that is fixed within an analytical tool (a column or a capillary) and that contributes to separation through the partitioning of the substance to be separated between the stationary phase and a fluid that is moving while in contact with the stationary phase.
- an analytical tool a column or a capillary
- the stationary phase also denotes the aggregate formed by the packing of these particles as well as the individual particles themselves.
- the stationary phase of the present invention contains a polymer that has in the main chain repeat units an aromatic ring that forms a portion of the main chain and a bipolar atomic group that forms a portion of the main chain.
- aromatic ring that forms a portion of the main chain means that this aromatic ring forms a structural element of the main chain of the polymer. Stated differently, this means that this aromatic ring has at least two substituents, and tracing along one of them leads to one terminal of the polymer and tracing along the other leads to the other terminal of the polymer.
- This aromatic ring includes benzene; condensed cyclic aromatic hydrocarbons such as naphthalene, phenanthrene, and pyrene; heterocyclic aromatic hydrocarbons such as thiophene and pyrrole; and selections from those in which a plurality of rings are connected by a single bond such as biphenyl.
- the positions of the two substituents are not limited, but the substitution patterns in the case of benzene can be exemplified by the 1,2-positions, 1,3-positions, and 1,4-positions; the substitution patterns in the case of naphthalene can be exemplified by the 1,4-positions, 1,5-positions, 2,5-positions, 2,6-positions, and 2,7-positions; and the substitution patterns in the case of biphenyl can be exemplified by the 4,4'-positions and the 3,3'-positions.
- the aromatic ring is preferably benzene, naphthalene, or biphenyl.
- the aromatic ring may have a substituent other than the polymer main chain, and this substituent can be exemplified by C 1-12 alkyl, C 1-12 alkoxy, cyano, halogen, hydroxy, amino, nitro, and so forth. Substitution by the methyl group or a halogen atom (F, Cl, Br, I) is preferred because there is little direct interaction for these substituents themselves and this substitution can influence the molecular discrimination of the polymer.
- the polymer used in the present invention contains a bipolar atomic group that forms a portion of the main chain.
- This bipolar atomic group that forms a portion of the main chain has, for example, a structure with the following formula. [C1]
- both of the two valences on X in formula (I) or (II) that are not assigned a bonding partner are structural elements of the main chain of the polymer. Stated differently, this means that tracing along one of them leads to one terminal of the polymer and tracing along the other leads to the other terminal of the polymer.
- Y when X is carbon, Y is oxygen (carbonyl group), sulfur (thiocarbonyl group), or nitrogen bearing one substituent (including oximes and hydrazones); when X is sulfur, Y is oxygen (sulfoxide, sulfone) or nitrogen bearing one substituent (sulfilimine, sulfoximine); and when X is phosphorus bearing one substituent, X is oxygen or nitrogen bearing one substituent.
- the carbonyl group, sulfoxide, and sulfone are preferred.
- bipolar atomic group With regard to the content of the bipolar atomic group, generally 1 to 3 and preferably 1 to 2 bipolar atomic groups are contained in 1 unit of the repeat units making up the polymer.
- This "repeat units making up the polymer” denotes the single monomer unit when the polymer is obtained by the polymerization of a single species of monomer and, when the polymer is obtained by the polymerization of two or more species of monomers, denotes, for example, the terephthalic acid/ethylene glycol dimer in the case of polyethylene terephthalate.
- the content in the present invention of the repeat units containing the aromatic ring and bipolar atomic group in the repeat units making up the polymer is generally 70 to 100 mol% and is preferably 90 to 100 mol% (not considering the terminals).
- This polymer can be specifically exemplified by polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene isophthalate, poly(2,2-dimethylpropan-1,3-diyl terephthalate), polyarylate, and poly-4-oxymethylbenzoyl, as well as by polysulfone (PS), polyethersulfone (PES), polycarbonate (PC), and polyetheretherketone (PEEK).
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PS polyethersulfone
- PC polycarbonate
- PEEK polyetheretherketone
- the molecular main chain In order to provide a good number of column stages as a column packing, the molecular main chain generally preferably has a high-mobility substructure such as -CH 2 -CH 2 -.
- the polymer used in the present invention is a polyester
- its synthesis may be carried out, for example, by a dehydration condensation between a carboxylic acid and an alcohol or phenol, or transesterification with an ester, or reaction with an acid halide.
- terephthalic acid for example, terephthalic acid, phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, the preceding substituted by the methyl group or a halogen atom on the aromatic ring, and their esters and halides can be used as the dicarboxylic acid, while for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 2,2-dimethylpropane-1,3-diol, 1,4-butanediol, 1,4-cyclohexanedimethanol, and 1,4-cyclohexanediol can be used as the diol component.
- An aromatic compound having a carboxylic acid or residue thereof and an alcohol or phenol in the molecule may also be used as a single monomer.
- the "polyester” described in Japanese Patent No. 3,858,509 which is a vinyl polymer having ester side chains, is not a polyester in the general sense or for the purposes of the present invention.
- the aromatic ring that forms a portion of the main chain is preferably 1,4-benzene, 1,3-benzene, 1,6-naphthalene, 1,7-naphthalene, or 1,5-thiophene.
- a peak broadening trend generally appears in chromatography when this ring is too large.
- the presence in the repeat units of a high-mobility substructure e.g., -CH 2 -CH 2 - and so forth, is preferred in order to provide a good number of column stages as a column packing.
- condensation polymers that use terephthalic acid or isophthalic acid as the carboxylic acid and ethylene glycol, propylene glycol, butylene glycol, or 2,2-dimethylpropane-1,3-diol as the dihydric alcohol, and poly-4-oxymethylbenzoyl, which is provided by the condensation of 4-hydroxymethylbenzoic acid or methyl 4-hydroxymethylbenzoate, are easily obtained and hence are preferred.
- PET which is the condensation polymer from terephthalic acid and ethylene glycol
- PBT which is the condensation polymer from terephthalic acid and butylene glycol
- the weight-average molecular weight of the polyester under consideration is 1,000 to 5,000,000 and is preferably 5,000 to 1,000,000. This range is preferred considering, for example, the solvent solubility of the polymer, prevention of particle aggregation when the polymer is supported on a carrier, inhibition of dissolution in the moving phase solvent, and maintaining the amount of bonding in the case of chemical bonding to a carrier.
- the optimal point will vary as a function of the type of polymer.
- the weight-average molecular weight can be measured by gel permeation chromatography (GPC) using polystyrene as the standard substance.
- the synthesis method can be, for example, an interfacial method in which a bisphenol is directly reacted with phosgene, or a transesterification method in which a bisphenol is reacted with diphenyl carbonate under solventless conditions.
- the weight-average molecular weight of the polycarbonate under consideration is 1,000 to 5,000,000 and is preferably 5,000 to 1,000,000.
- polymer used in the present invention is a polyethersulfone
- polymer from 4-chloro-4'-hydroxydiphenylsulfone can be provided as a typical example.
- the weight-average molecular weight of the polyethersulfone is 1,000 to 5,000,000 and is preferably 5,000 to 100,000.
- the polymer used in the present invention is a polysulfone
- its weight-average molecular weight is 1,000 to 5,000,000 and is preferably 5,000 to 100,000.
- these polymers may have a strongly polar atomic group, e.g., the carboxyl group, in terminal position.
- a strongly polar atomic group e.g., the carboxyl group
- Such an atomic group frequently causes the chromatographic efficiency to decline through a strong adsorption known as non-specific adsorption. Deactivation by some chemical treatment is thus preferred.
- the carboxyl group may be converted to the ester, and, for example, diazomethane or trimethylsilyldiazomethane is frequently used for this purpose. Reaction with an amine and a so-called condensation agent, e.g., DCC, may also be performed.
- an excellent chromatogram can be obtained through the addition of a small amount of an ionic additive, for example, an amine, an acid, or their mixture, to the moving phase.
- an ionic additive for example, an amine, an acid, or their mixture
- the developing solvent is a solvent that can natively dissolve the polymer or is a mixed solvent containing such a solvent, all or a portion of the polymer may be dissolved and the functionality as a column will then be impaired. Due to this, the polymer according to the present invention is preferably an insolubilized polymer.
- the candidate set of applicable developing solvents can be broadened when the polymer has been insolubilized.
- insolubilization may be performed by a method in which the polymer is chemically bonded to the surface of a carrier.
- Insolubilization can be carried out by bonding the polymer to a reactive atomic group that has been bonded, using a spacer such as a silane coupling agent, to the surface of the carrier, e.g., silica gel.
- a spacer such as a silane coupling agent
- any carbonyl group in the polyester forms the amide and insolubilization is made possible as a result by the bonding of the polymer to the silica gel surface.
- an epoxy group-bonded silica gel will bond the polymer by reaction with terminal carboxylic acid groups in the polyester.
- a substituent capable of bonding to the other party may be introduced into the carrier and/or polymer.
- a polyethersulfone have a terminal chlorine atom may be insolubilized by bonding to the carrier, e.g., silica gel, by substitution of the chlorine with an amino group.
- a polyester may be bonded, for example, to a hydroxyl group-bonded silica gel in the presence of a suitable acid catalyst such as a sulfonic acid.
- a polyethersulfone may also have a phenolic hydroxyl group in terminal position, and this may be converted to the phenolate with a suitable base, such as an alkoxide, followed by reaction with a halomethylphenyl group- or epoxy group-bonded silica gel to effect bonding to the silica gel by a substitution reaction and bring about insolubilization.
- a suitable base such as an alkoxide
- the polymer can be bonded on the silica gel by having bonded an atomic group capable of participating in the polymerization to the silica gel surface in advance.
- the polymer itself can also be insolubilized without creating a chemical bond with the carrier, e.g., silica gel.
- insolubilization can be brought about by crystallization by execution of just a heat treatment. Insolubilization may also be brought about by the formation of intermolecular crosslinking of unspecified structure by exposure to high-energy electromagnetic radiation, e.g., ultraviolet radiation or gamma-radiation, or exposure to particle radiation such as electron radiation.
- An insoluble crosslinked polymer can also be made by the addition to the monomer of a suitable amount of monomer having multiple polymerizable functional groups (for example, the vinyl group, silyl group, and so forth).
- the reaction that forms the polymer main chain may be different from the crosslinking reaction.
- the average degree of polymerization of the polymer used in the present invention is at least 5 and is preferably at least 100.
- the upper limit there are no particular limitations since no problems are caused by a high degree of polymerization, but the upper limit is generally not more than 10,000,000.
- the average degree of polymerization can be measured by GPC.
- the average degree of polymerization prior to treatment of the polymer is the relevant value when, as described above, the polymer is chemically bonded or insolubilization is carried out by crystallization through a heat treatment.
- the average degree of polymerization is estimated in those instances where the degree of polymerization of the polymer does not fit, such as when the monomer is polymerized on the carrier.
- the chemically bonded polymer is assumed to have the same degree of polymerization as the not-chemically-bonded polymer of the polymerizate, and after the polymerization reaction on the carrier, washing is first performed with a solvent that dissolves only low molecular weight material, this is followed by washing with a solvent that dissolves the polymer, and GPC is carried out on the extracted polymer.
- the following method can be used in those instances in which even this assumption is problematic: using a reagent that dissolves the carrier under mild conditions (for example, a methanol solution of ammonium hydrogen fluoride when the carrier is silica gel), dissolution is carried out until there are no atomic groups bonded to the carrier surface, the obtained eluate is treated with, for example, hexamethyldisilazane, and the average degree of polymerization is then measured by GPC analysis.
- a reagent that dissolves the carrier under mild conditions for example, a methanol solution of ammonium hydrogen fluoride when the carrier is silica gel
- dissolution is carried out until there are no atomic groups bonded to the carrier surface
- the obtained eluate is treated with, for example, hexamethyldisilazane, and the average degree of polymerization is then measured by GPC analysis.
- terminal group analysis is also possible depending on the structure of the polymer terminals.
- the terminal is a carboxylic acid
- an atomic group containing an indicator element may be introduced by, for example, esterification or carbamoylation, and the amount of introduction of this element may then be analyzed; however, when the silica gel surface has been modified with the amino group, its inactivation is required in advance using an amino group-selective chemical treatment.
- the appropriate analytical method as a function of, for example, the bonded polymer and the atomic groups already bonded to its carrier.
- a porous stationary phase can be made by supporting the polymer on a particulate or monolithic carrier.
- the polymer can itself be utilized in the form of porous spherical or amorphous particles, a porous single body or so-called monolith having continuous pores, or a porous film.
- the "porous" referenced for the present invention refers to having a specific surface area for the surface, as measured by the BET method using nitrogen adsorption, of 5 to 1000 m 2 /g and preferably 10 to 500 m 2 /g.
- a specific surface area for the stationary phase in the indicated range is advantageous for the separation of low molecular weight compounds and is preferred from the standpoint of preventing tailing.
- a carrier with the desired specific surface area should be selected since the specific surface area of the stationary phase corresponds to the specific surface area of the carrier used.
- the carrier for example, silica gel, can be prepared by selecting suitable products.
- a variation in the specific surface area pre-versus-post-support in excess of the margin of error generally does not occur, and as a consequence the specific surface area of the stationary phase can be considered to be the same as the specific surface area of the carrier used.
- the polymer is executed as a particulate or monolith
- methods for adjusting the specific surface area of the stationary phase can be exemplified, considering the case of suspension polymerization, by raising the specific surface area by the addition as a diluent of an organic solvent that dissolves in the monomer mixture, is inert to the polymerization reaction, and does not dissolve the produced polymer.
- this carrier can be exemplified by porous organic carriers and porous inorganic carriers, wherein porous inorganic carriers are preferred.
- High molecular weight substances selected from, for example, polystyrenes, poly(meth)acrylamides, and poly(meth)acrylates are suitable porous organic carriers, while suitable porous inorganic carriers are, for example, silica gel, alumina, zirconia, titania, magnesia, glass, kaolin, titanium oxide, silicate, and hydroxyapatite.
- Silica gel, alumina, and glass are preferred carriers.
- the average particle diameter of this carrier is generally 0.1 to 100 ⁇ m and is preferably 1 to 50 ⁇ m. Its average pore diameter is generally 10 to 10,000 ⁇ and is preferably 50 to 1,000 ⁇ .
- the specific surface area of the carrier is generally 5 to 1,000 m 2 /g and is preferably 10 to 500 m 2 /g. In those instances in which the polymer is supported on a carrier, the average particle diameter of the stationary phase can be considered to be the same as the average particle diameter of the carrier used since a variation in the specific surface area pre-versus-post-support in excess of the margin of error generally does not occur.
- a chemical treatment of its surface can suppress excessive adsorption of the separation target to the carrier itself and can facilitate the chemical bonding of the polymer.
- the chemical treatment can be exemplified by treatment with a silane coupling agent or aminopropylsilane as described for the insolubilization methodologies.
- the average thickness of the polymer (amount supported per g of carrier/specific surface area of the carrier) supported on the carrier is generally 2/10 5 to 2/10 7 ( ⁇ m) and is preferably 4/10 5 to 5/10 7 . A trend toward sharper peaks occurs in the indicated range, which is thus preferred.
- the method for supporting the polymer on the particulate or monolithic carrier can be exemplified by methods in which the polymer is dissolved in a solvent, and, after the carrier has been, for example, coated, sprayed, or immersed, the solvent is removed using reduced pressure or a traversing gas current, leaving the polymer on the carrier surface.
- the solvent may be selected from suitable solvents capable of dissolving the polymer used, and, for the case of PET, can be exemplified by 1,1,1,3,3,3-hexafluoro-2-propanol, while for the case of a polyethersulfone the solvent can be exemplified by dichloromethane.
- the precursor for the polymer is impregnated into the carrier, along with a suitable catalyst as necessary, and polymerization is then carried out.
- Methods in which support on the carrier is effected by chemical bonding are additional examples of the method for supporting the polymer on the particulate or monolithic carrier.
- the same methods as described above for polymer insolubilization can be used to effect support on the carrier by chemical bonding.
- the percentage (%) of the mass parts of the polymer present in 100 mass parts of the stationary phase is preferably 1 to 50% and more preferably is 10 to 30%. Observing this percentage makes it possible to avoid peak broadening and an unnecessary strengthening of the retention while bringing about a favorable expression of the adsorptive capacity of the polymer, and hence is preferred.
- Suspension polymerization is an example of a method for making the polymer itself into a stationary phase of porous spherical or amorphous particles.
- an already prepared solution of the polymer is suspended in a liquid that is immiscible with this solution and the solvent is gradually removed by diffusion, or the polymer is precipitated using a precipitant, or the solution is gelled by changing the temperature.
- it is effective to add in advance in a suitable amount a substance that is not compatible with the polymer but which dissolves in the solvent that is dissolving the polymer, and to wash out and extract this substance after the particles have been solidified.
- Porosity may also be generated by inducing spinodal decomposition during polymerization or during temperature change-induced gelation.
- the average particle diameter of the stationary phase is generally 0.1 ⁇ m to 1,000 ⁇ m and is preferably 1 ⁇ m to 100 ⁇ m.
- the average particle diameter of the stationary phase is generally 0.1 ⁇ m to 1,000 ⁇ m and is preferably 5 ⁇ m to 500 ⁇ m and is more preferably 10 ⁇ m to 200 ⁇ m. This range is preferred in terms of the balance between an excellent column efficiency and the fluid permeability of the packing layer.
- the average particle diameter refers to the diameter in the case of a spherical shape, but in the case of an amorphous particle represents the diameter of the sphere equal to the volume of the particle.
- the average particle diameter can be measured using an instrument that performs the measurement using a micrographic image, for example, the Mastersizer 2000E from Malvern.
- a porous monolith can also be made by a phase separation process when the conditions described for the methods for forming porous particles are applied, for example, in a suitable container and without generating a suspended state.
- the polymer may also be supported on a carrier that is already in the form of a monolith. The same materials as used for the previously described carriers can be used as the material of a carrier monolith.
- the aspect ratio is not more than 2 and preferably not more than 1.5. Since closer to spherical is better, the lower limit is not particularly limited down to 1.
- the aspect ratio may be measured as follows.
- the sample, having been randomly broadcast on the observation stage, is observed from directly above with an electron microscope or optical microscope; a field is randomly selected in which at least 10 independent (not in contact with or overlapping with any other particle) primary particles are observed; the major axis and minor axis (the length of the longest portion orthogonal to the major axis) is determined for each of the independent primary particles in the field; and the ratio between the two is taken to be the aspect ratio of the individual particle.
- the arithmetic average of the aspect ratios for all the independent primary particles in the field is made the aspect ratio in the present invention.
- a primary particle is a particle for which a particle-to-particle interface can be clearly and distinctly observed.
- the observation is ordinarily carried out with dispersal on the sample stage sufficient to avoid primary particle overlap. However, it is difficult to avoid incidental overlap, and in addition bulk particles in which a plurality of primary particles are aggregated may also be present, but these are excluded from the observation target.
- the stationary phase of the present invention can be used in supercritical fluid chromatography (SFC) and in liquid chromatography such as HPLC and so forth.
- silica gels having an average particle diameter of 5 ⁇ m and a pore diameter of 120, 300, or 700 ⁇ , were aminopropylated using the following procedure. 14 g of the silica gel was vacuum dried at 100°C followed by dispersion in 150 mL of toluene, and a portion of the toluene (approximately 30 mL) was removed by distillation until the cloudiness in the condensate had disappeared. 7 mL of aminopropyltriethoxysilane was added to the silica gel dispersion, and approximately 200 mL was distilled off over 8 hours while making supplementary additions of about 200 mL toluene in suitable aliquots. After the liquid had been cooled, the silica gel was collected on a glass filter and was washed once with 70 mL of toluene and twice with 70 mL of dichloromethane; this was followed by vacuum drying.
- FIG. 1 A photomicrograph of the obtained silica gel (the silica gel with a pore diameter of 120 ⁇ ) is given in FIG. 1 .
- the average of the aspect ratio was about 1.0 for 22 particles photographed on the randomly selected field.
- the obtained powder was dispersed in 30 mL of methanol to which a solution of 63 mg of ammonium bicarbonate dissolved in water had been added and was recovered by filtration on a glass filter and then washed 4 times with 50 mL of methanol. After drying, the product was washed an additional 3 times with 50 mL of NMP, followed by dispersion in a mixture of 15 mL of methanol and 10 mL of toluene, addition of 0.5 mL of a 10% hexane solution of trimethylsilyldiazomethane, and standing overnight. This was followed by washing with a suitable amount of methanol and vacuum drying.
- the specific surface area of the obtained poly(4-oxymethylbenzoyl)-bonded silica gel was taken to be 98 m 2 /g and its average particle diameter was taken to be 5 ⁇ m.
- the obtained poly(4-oxymethylbenzoyl)-bonded silica gel was slurry packed as the stationary phase into a 2.1 mm ⁇ x 150 mm column and terphenyl isomers and triphenylene were separated using liquid chromatographic conditions.
- the separation of the terphenyl isomers and triphenylene by HPLC on the polyoxymethylbenzoyl stationary phase is shown in FIG. 2 .
- the peak sequence is ortho isomer, meta isomer, para isomer, and triphenylene.
- the column size was 2.1 mm ⁇ x 150 mm, and the moving phase was 0.21 mL/min of 9 : 1 v/v hexane/2-propanol.
- silica gel with a pore diameter of 300 ⁇ was treated with glycidoxypropyltriethoxysilane in place of the aminopropyltriethoxysilane.
- the temperature was held at 93°C and the toluene distillation was not performed.
- the carbon content in the obtained silica gel was 1.21 mass%.
- Dispersal with 40 mL of NMP and collection by filtration was carried out an additional 3 times, followed by washing in succession with 40 mL of acetone, 40 mL of methanol, and 40 mL of an equivolume mixture of hexane/acetone and drying under a vacuum.
- the carbon content of the obtained silica gel was 6.76 mass%.
- the polymer content in the product was calculated to be 7.9 mass% from the fact that the carbon content of the silica gel prior to the supporting process was 1.21 mass%.
- the specific surface area of the obtained stationary phase was taken to be 98 m 2 /g and its average particle diameter was taken to be 5 ⁇ m.
- This stationary phase is packed into a column (4.6 mm ⁇ x 150 mm) by the slurry method; examples of the analysis of aromatic hydrocarbons by HPLC and SFC are shown in FIG. 3 .
- the upper chromatogram in FIG. 3 is HPLC at 25°C using 1 mL/min of hexane/2-propanol (100 : 1 v/v). From the left, the peaks are o-terphenyl, m- and p-terphenyl (overlapping), and triphenylene. Detection was carried out by UV at 254 nm.
- the lower chromatogram in FIG. 3 is SFC by CO 2 /methanol (97 : 3 v/v). It was carried out at flow rate: 4 ml/min, temperature: 40°C, and back pressure: 150 bar. From the left, the peaks are o-terphenyl, m-terphenyl, p-terphenyl, and triphenylene. Detection was carried out by UV at 254 nm.
- the specific surface area of the obtained stationary phase was taken to be 35 m 2 /g and its average particle diameter was taken to be 5 ⁇ m.
- the carbon content by elemental analysis of the obtained stationary phase was 11.65%.
- the PES content of the product was calculated at 12.4 mass% from the fact that the carbon content of the silica gel prior to the supporting process was 3.7 mass%.
- the specific surface area of the obtained stationary phase was taken to be 320 m 2 /g and its average particle diameter was taken to be 5 ⁇ m.
- the silica gel dispersion was cooled to around room temperature, after which 6.18 g of chloromethylphenylethyltrimethoxysilane and 0.33 g of acetic acid were added and 30 mL of toluene was gradually distilled out at a bath temperature of 125°C. After the reaction solution had been cooled, the silica gel was filtered onto a glass filter and was washed 4 times with 30 mL of toluene and 3 times with 40 mL of methanol and then dried under a vacuum.
- the silica gel was collected from the dispersion by filtration on a glass filter and was washed 5 times with 30 mL of DMSO, 3 times with 30 mL of dichloromethane-methanol (9 : 1 v/v), and finally 5 times with 30 mL of methanol and dried under a vacuum.
- the carbon content of the obtained stationary phase was 2.56 mass%, and the PES content in the product was calculated at 1.18 mass% from the fact that the carbon content of the chloromethylphenylethylsilane-treated silica gel was 1.85 mass%.
- the specific surface area of the obtained stationary phase was taken to be 98 m 2 /g and its average particle diameter was taken to be 5 ⁇ m.
- trimethylsilane-treated silica gel with
- the silica gel was a powder in each case; there was no visible difference from prior to coating with the PBT; and the specific surface area and average particle diameter were also taken to be the same. Since elution of the polymer into the washing solvent and separation of the polymer from the silica gels were not observed, almost the entire amount of the polymer was thought to be supported on the silica gels.
- FIG. 4 gives an example of separation by HPLC and SFC on the stationary phase prepared using the aminopropylsilane-treated silica gel with a pore diameter of 700 ⁇ .
- the upper chromatogram in FIG. 4 is HPLC at 25°C using 1 mL/min of hexane/2-propanol (100 : 1 v/v). From the left, the peaks are o-terphenyl, m-terphenyl, p-terphenyl, and triphenylene. Detection was carried out by UV at 254 nm.
- the lower chromatogram in FIG. 4 is SFC by CO 2 /methanol (97 : 3 v/v). It was carried out at flow rate: 4 mL/min, temperature: 40°C, and back pressure: 150 bar. From the left, the peaks are o-terphenyl, m-terphenyl, p-terphenyl, and triphenylene. Detection was carried out by UV at 254 nm.
- the carbon content in the obtained powder was 17.27 mass%, and a PBT content in the product of 24.9 mass% was calculated from the fact that the carbon content in the aminopropylsilane-treated silica gel was 1.3 mass%.
- the specific surface area of the obtained stationary phase was taken to be 98 m 2 /g and its average particle diameter was taken to be 5 ⁇ m.
- FIG. 5 shows a chromatogram obtained with the obtained stationary phase packed into a column as described in Example 2.
- FIG. 5 is SFC by CO 2 /methanol (97 : 3 v/v). It was carried out at flow rate: 4 mL/min, temperature: 40°C, and back pressure: 150 bar. From the left, the peaks are o-terphenyl, m-terphenyl, p-terphenyl, and triphenylene. Detection was carried out by UV at 254 nm.
- FIG. 6 shows an example of SFC carried out using a column packed with the obtained stationary phase.
- FIG. 6 is SFC by CO 2 /methanol (97 : 3 v/v). It was carried out at flow rate: 4 mL/min, temperature: 40°C, and back pressure: 150 bar. From the left, the peaks are o-terphenyl, m-terphenyl, p-terphenyl, and triphenylene. Detection was carried out by UV at 254 nm.
- FIG. 7 shows an example in which separation on a stationary phase of the present invention is compared with separation on a 2-ethylpyridine separation agent, which has entered into general use for SFC.
- the SFC separation of acetyl-substituted anthracenes and phenanthrenes was evaluated for a column (0.46 mm ⁇ ⁇ 15 cm in each case) packed with Viridis Silica 2-Ethylpyridine 5 ⁇ m from Waters (upper chromatogram) and a column packed with the stationary phase of Example 10 (lower chromatogram).
- the SFC was carried out as follows: moving phase: CO 2 -methanol (9 : 1 v/v), flow rate: 4.0 mL/min, temperature: 40°C, and back pressure: 150 bar.
- the stationary phase of the present invention exhibits a better separation performance for substitutional isomers with similar structures than does 2-ethylpyridine. It is thought that, because the polymer that incorporates aromatic rings and bipolar atomic groups provides a regular arrangement to a certain degree, an adsorption field sensitive to molecular shape is formed.
- Example 8 the product obtained in Production Example 4 was dissolved in hexafluoro-2-propanol and supported on trimethylsilane-treated silica gel with a pore diameter of 120 ⁇ .
- the specific surface area of the obtained stationary phase was taken to be 320 m 2 /g and its average particle size was taken to be 5 ⁇ m.
- the obtained stationary phase was packed in a column having an internal diameter of 4.6 mm and a length of 150 mm.
- SFC sulfur chloride
- the o-terphenyl, m-terphenyl, p-terphenyl, and triphenylene eluted at 1.15 minutes, 1.83 minutes, 1.95 minutes, and 7.61 minutes, respectively, and an excellent separation was obtained except for the m- and p-terphenyl isomers.
- Example 11 the product obtained in Production Example 5 was supported using dichloromethane on trimethylsilane-treated silica gel that had a pore diameter of 120 ⁇ .
- the specific surface area of the obtained stationary phase was taken to be 320 m 2 /g and its average particle size was taken to be 5 ⁇ m.
- the obtained stationary phase was packed in a column having an internal diameter of 4.6 mm and a length of 150 mm, and monoacetyl-substituted anthracenes and phenanthrenes were then analyzed under HPLC conditions (25°C, 1.0 mL/min of hexane/2-propanol 90 : 10 (v/v)): the 9-acetylanthracene eluted at 4.5 minutes; the 9-acetylphenanthrene eluted at 5.8 minutes; the 3-acetylphenanthrene eluted at 6.4 minutes; and the 2-acetylanthracene and 2-acetylphenanthrene eluted overlapped at 8.3 minutes.
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EP3395424A1 (fr) * | 2017-04-28 | 2018-10-31 | Shimadzu Corporation | Procédé de séparation et procédé d'analyse |
CN110139891A (zh) * | 2017-01-06 | 2019-08-16 | 住友化学株式会社 | 树脂微粒的制造方法、树脂粒子 |
US11731106B2 (en) * | 2019-10-02 | 2023-08-22 | Shimadzu Corporation | Column packing material for supercritical fluid chromatography, column for supercritical fluid chromatography and preparation method therefor |
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WO2016152996A1 (fr) * | 2015-03-24 | 2016-09-29 | 株式会社ダイセル | Phase stationnaire pour chromatographie à fluide supercritique |
JP6810039B2 (ja) * | 2015-07-31 | 2021-01-06 | 株式会社ダイセル | 超臨界流体クロマトグラフィー用の固定相 |
EP3327071B1 (fr) * | 2015-08-10 | 2020-04-29 | Kyoto University | Particule poreuse constituée de polymère organique, procédé de production d'une particule poreuse constituée de polymère organique |
WO2017026424A1 (fr) * | 2015-08-10 | 2017-02-16 | 国立大学法人京都大学 | Particule poreuse, procédé de production de particule poreuse, et copolymère séquencé |
JP6813247B2 (ja) | 2016-03-23 | 2021-01-13 | 株式会社ダイセル | クロマトグラフィー用の固定相 |
JP6863816B2 (ja) * | 2017-04-28 | 2021-04-21 | 昭和電工マテリアルズ・テクノサービス株式会社 | 超臨界流体クロマトグラフィー用カラム充填剤、超臨界流体クロマトグラフィー用カラム及びそれらの製造方法 |
JP7144176B2 (ja) * | 2018-04-13 | 2022-09-29 | 株式会社島津製作所 | 抽出物の回収方法および分析方法 |
CN112138638B (zh) * | 2020-09-18 | 2021-08-13 | 北京理工大学 | 一种脂肪族聚碳酸酯的应用 |
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US4822492A (en) * | 1984-09-28 | 1989-04-18 | Uop | Latex polymer bonded crystalline molecular sieves |
JP3397255B2 (ja) | 1993-07-30 | 2003-04-14 | 直弘 曽我 | 無機系多孔質体の製造方法 |
US6066258A (en) * | 1997-12-05 | 2000-05-23 | Transgenomic, Inc. | Polynucleotide separations on polymeric separation media |
JP2002506426A (ja) | 1997-04-25 | 2002-02-26 | トランスジエノミツク・インコーポレーテツド | 非多孔質ポリマービーズ上でのポリヌクレオチド分離 |
JP3858509B2 (ja) | 1999-02-26 | 2006-12-13 | 昭和電工株式会社 | 改質された充填剤、その改質方法及びそれを用いたクロマトグラフィー用カラム |
US20020187557A1 (en) * | 2001-06-07 | 2002-12-12 | Hobbs Steven E. | Systems and methods for introducing samples into microfluidic devices |
JPWO2005085835A1 (ja) * | 2004-03-04 | 2008-01-24 | ダイセル化学工業株式会社 | 光学異性体用分離剤 |
ES2408655T3 (es) * | 2004-09-23 | 2013-06-21 | Tripath Imaging, Inc. | Recubrimientos poliméricos policatiónicos para inmovilizar muestras biológicas |
JP5003868B2 (ja) * | 2006-09-28 | 2012-08-15 | Jsr株式会社 | 有機ポリマー粒子およびその製造方法 |
ATE550367T1 (de) * | 2008-01-25 | 2012-04-15 | Kaneka Corp | Verfahren zur herstellung von polyalkylenoxid |
JP2010137207A (ja) * | 2008-12-15 | 2010-06-24 | Hitachi High-Technologies Corp | ミックスモード型吸着剤 |
EP4016075A1 (fr) * | 2012-05-23 | 2022-06-22 | Daicel Corporation | Agent de séparation |
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CN110139891A (zh) * | 2017-01-06 | 2019-08-16 | 住友化学株式会社 | 树脂微粒的制造方法、树脂粒子 |
EP3567071A4 (fr) * | 2017-01-06 | 2020-07-29 | Sumitomo Chemical Company, Limited | Procédé de production de microparticules de résine et particules de résine |
US11230628B2 (en) | 2017-01-06 | 2022-01-25 | Sumitomo Chemical Company, Limited | Resin microparticle production method and resin particles |
EP3395424A1 (fr) * | 2017-04-28 | 2018-10-31 | Shimadzu Corporation | Procédé de séparation et procédé d'analyse |
US11731106B2 (en) * | 2019-10-02 | 2023-08-22 | Shimadzu Corporation | Column packing material for supercritical fluid chromatography, column for supercritical fluid chromatography and preparation method therefor |
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EP2876439B1 (fr) | 2021-06-09 |
EP2876439A4 (fr) | 2015-07-08 |
JP6342328B2 (ja) | 2018-06-13 |
CN104471387A (zh) | 2015-03-25 |
CN104471387B (zh) | 2016-08-24 |
JPWO2014017280A1 (ja) | 2016-07-07 |
US20150182943A1 (en) | 2015-07-02 |
US9327269B2 (en) | 2016-05-03 |
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